Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



tam-WI United States Patent DETERGENT SULPHONIC ACID AND SUL- PHATESALTS OF CERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheimer, New York, N.Y.

No Drawing. Application May 24, 1956, Serial No. 586,929

6 Claims. (Cl. 260-459) This invention relates to novel compositions andto methods for making them. In one of its more specific aspects, theinvention is directed to methods of making and to novel derivatives of acertain class of starting materials. Said starting materials are aminocarboxylic acid metal salts, which I shall hereinafter refer to as aminoacid metal salts.

Said amino acid metal salts are useful as surface active agents, areemployed as starting materials in the practice of this invention, andhave the following general Formula I:

Y R-N-Yl .a R2-COOIvI in which R is a hydrocarbon radical of at least 6carbon atoms and preferably 6-18 carbon atoms, and for most purposes Ris preferably such a radical which may be either aliphatic and straightor branch chain or cycloaliphatic or aliphatic-aromatic, with thealiphatic portion being attached to an aromatic nucleus and having atleast 3 carbon atoms; Y and Y1 are each selected from the classconsisting of Re and R2COOM; R2 is an organic group selected from theclass consisting of (a) aliphatic, aromatic or aromatic-aliphatichydrocarbon groups of 1- 12 carbon atoms, such as CH2, C2H4, CaHs--,CaHs CsHro CsH, Cal-I4 CsH4CH2-, (b) hydroxy substituted aliphatichydrocarbon groups of 1-12 carbon atoms, illustrative examples of whichare -CHzCHOHCH2 (c) aliphatic ether groups, each of said groups havingat least one ether oxygen linkage therein and otherwise beinghydrocarbon of 2-12 carbon atoms, illustrative examples of which are (d)aliphatic ether groups, each of said group having at least one etheroxygen linkage therein and otherwise being, hydroxy substitutedhydrocarbon of 2-12 carbon atoms, illustrative example of which is Re isselected from the class consisting of monovalent radicals otherwisedefined in (a)-(d), examples of which are --CH3, -C2H5, CsH7, -C4H9,C5H11, C6H11, -C6H5, CsI-I4CH3, --C2H4OH, CH2CHOHCH2OH etc., --C2H4OCH3,etc.; M is an alkali metal and preferably sodium or potassium; and A isselected from the class consisting of halogens and hydroxyl (OH) andpreferably being C1 or OH.

It is to be understood, of course, that Formula I as before set forth ismeant to include throughout the present "ice description and claims suchsalts, as well as inner salts or anhydrides, such as for example:

Such amino acid metal salts may be prepared in a number of differentways well known to the art:

For example, 1 mole of RNH2 may be reacted with one mole of RsCl andwith the use of caustic soda produced HCl is removed to provide which,in turn, is reacted with an equimolecular proportion of RsCl and theproduced HCl is removed to provide Ra One mole of /Ra RN\ is reactedwith one mole of an alkali metal salt of monochlormonocarboxylic acideither in aqueous or alcohol medium to provide a starting material:

If desired the Cl of such starting materials may be substituted by OH toprovide equivalent starting materials by reacting it with an alkalimetal hydroxide MOH, whereby Cl is substituted by OH and MCI is formed.

Or, 1 mole of RNH2 may be reacted with 1 mole of amonohalomonocarboxylic acid together with 2 moles of caustic soda toprovide which in turn may be reacted with an equimolecular proportion ofa monohalomonocarboxylic acid together with a dimolecular proportion ofcaustic soda to provide RzCOOM R N Rr-COOM which may also be produced byreacting 1 mole of R-NH2 with 2 mols of a monohalomonocarboxylic acidtogether with 4 moles of caustic soda. Then 1 mole of reaction with MOH.

Or, 1 mole of Rr-CO 0M may be reacted with 1 mole ofmonochlormonohalocarboxylic acid to provide:

Rz-COOM RNRz-OOOM G RzCOOM which if desired may have its Cl replaced byOH by the use of caustic soda.

The monohalocarboxylic acids employed are preferably monochloracetic,monochlorpropionic, monochlorlactic, and the alkali employed ispreferably NaOH or KOi-I.

The following Examples A-1 and A to 1-1 are given merely by Way ofillustrating in general methods which may be employed for producingexamples of starting materials employed in the practice of thisinvention, such methods being known to the art and, as such, are no partof this invention.

EXAMPLE A 1 mole of C12H25NH2 is reacted with 1 mole of methyl chlorideand then reacted with NaOH to remove the HCl formed to provide and 1mole proportion thereof is reacted with 1 mole of methyl chloride andthen reacted with NaOH to provide Ce aand then 1 mole proportion thereofis reacted with 1 mole of sodium salt of monochloracetic acid toprovide:

EXAMPLE B 1 mole of hexyl benzyl amine:

H CeH1s-N CH9CsHs is reacted with 1 mole of monochlorlactic acid,together with 2 moles of sodium hydroxide to provide:

CHf-CHOH-C O ONEL OoHrr-N OHPCQH then 1 mole thereof is reacted with onemole of sodium salt of monochloracetic acid to provide:

hereinafter known as product B and which may be reacted with anequimolecular proportion of NaOH to replace Cl w1th OH and ishereinafter known as product B-l.

EXAMPLE C 1 mole of lauryl phenyl amine:

is reacted with 1 mole of monochlorethoxyacetic acid together with 2moles of caustic soda to provide:

then 1 mole thereof is reacted with 1 mole of sodium salt ofmonochloracetic acid to-provide:

O H2-C O O Na C n 25 NCaHs 0211.10 OHgOOONa hereinafter known as productC which may be treated with an equimolecular proportion of caustic sodato replace the Cl to OH to provide product C-l.

EXAMPLE D 1 mole of C9H19C6H4NH2 may be reacted with ethylenechlorhydrin in the presence of caustic soda to provide:

and 1 mole thereof may be reacted with 1 mole of acetic acid togetherwith 2 moles of caustic soda to provide:

CH2O o ONa O9HIB CBH4N Cal-LOH Said compound is then reacted with anequimolecular proportion of sodium salt ofmonochloracetic acid toprovide:

CH5G o 0 Na C 9H1n-CaH4N CHzC O ONa I rELrOH hereinafter known asproduct D which may be treated with equimolecular proportion of NaOH toreplace Cl with OH and is hereinafter known as product D-l.

EXAMPLE E hereinafter known as product E which may bereacted withequimolecular proportion of NaOH to replace Cl with OH to provideproduct El.

EXAMPLES F and G 1 mole of C12H2s-NH2 is reacted in the presence of 2moles of NaOH with the following respective compounds:

ClCsH4COOI-I and C1CHaCsH4COOH to provide the. respective compoundswhich may be to spectively reacted with equimolecular proportion ofmonochloracetic acid in the presence of dimolecular proportion of NaOH,and the resulting compounds subsequently reacted with equimolecular proportion of sodium salt of monochlorpropionic acid to provide:

elmo ONa C nHss-N-CHz- C O ONn l C aH4C 0 ONa and 0 54-0 0 ONa C 9H,-N-CH2C 0 ONE] CHgCsHs-C OONa Cl hereinafter known as products F and Grespectively, which may be reacted with equimolecular proportion of NaGHto replace Cl with OH to provide compounds hereinafter known as productsF-l and G-l respectively.

EXAMPLE H 1 mole of is reacted with glycerine chlorhydrin and with theuse of caustic soda, and the resultant organic reaction product isreacted with an equimolecular proportion of sodium salt ofmonochloracetic acid to provide:

CHzCHOHCHnOH hereinafter known as Product H which may be reacted withequimolecular proportion of NaOH to replace Cl with OH and provideproduct H l.

EXAMPLE I 1 mole of C9H19-CsI-I4-NH2 is reacted with 2 moles ofmonochloracetic acid, together with 4 moles of KOH to provide:

and 1 mole thereof is reacted with 1 mole of potassium saltmonochlorpropionic acid to provide:

This compound, hereinafter known as product I, may be reacted with 1mole KOH to replace the Cl thereof with OH to provide compoundhereinafter known as product H.

The radical R of all of the formulas hereinbefore and hereinafter setforth is that hereinbefore defined in connection with Formula I. Insteadof employing monochloracetic acid, any other appropriatemonohalomonocarboxylic acid, such as monochlorpropionic, monochlorlacticacids, etc. may be employed. Thus, by merely substituting the particularmonohalomonocarboxylic acid for those used in the production of theparticular compounds hereinbefore set forth, and/or by employing thevarious radicals and groups for R6 and R2 but within the definitionsthereof as heretofore defined, a very great number of products X,examples of which are products A to I and Al to I-l, are amino acidmetal salts, which may be employed as starting materials or reactants inthe practice of this invention.

Prior to this invention, it'was known that cationic surface activeagents and anionic surface active agents when together in aqueoussolution resulted in the production or formation of water insolublecompounds; and that adding an anionic surface active agent to an aqueoussolution of another anionic surface active agent resulted in a merephysical combination of said agents and that no reaction would occurbetween them.

Said amino acid metal salts normally behave anionically in aqueoussolutions having a pH above 7, and consequently it was expected thatsaid amino acid metal salts when in aqueous solution together withanionic surface agents that they Would be combined physically only andthat no chemical reaction would occur therebetween. In the course of myexpe-rimentations, I have discovered that said amino acid metal saltscould be reacted with certain anionic surface active agents at a pHabove 7 to produce water-soluble reaction products. Not only did I makesaid discovery, but I further discovered that water solutions of suchreaction products had viscosities greater than corresponding aqueoussolutions of the amino acid metal salts" and also exhibited betterfoaming characteristics than did said amino acid metal salts in very lowdilutions under extreme water hardness conditions. Said reactionproducts are non-toxic and non-irritating to the human skin. They havebeen found eminently useful as general utility detergents, such as forcar washing, dish washing, clothes washing, etc. Said amino acid metalsalts, as Well as compounds of Formula II hereinafter described and suchamino acid metal salts and compounds of Formula II in mere physicalmixtures, when used as components of shampoos cause stinging andsometimes slight irritation of the eyes when such shampoos were used andwater solutions thereof accidentally reached the eyes. I have furtherdiscovered that the reaction prodnets of this invention causedpractically no irritation or stinging of the eyes when employed ascomponents of shampoos.

According to this invention, one or a combination of two or more of saidamino acid metal salts of the general structural Formula I are reactedwith one or a combination of two or more anionic surface active agentsof the following general structural Formula II to provide novel,water-soluble compounds having the following general structural FormulaIII, and having high wetting, detergency, and surface active propertiesand capable of providing voluminous and stablefoams in aqueoussolutions, and which aqueous solutions are substantially non-irritatingto the skin and eyes of normal human beings.

Formula II R3XM Formula III Y R--NYl l\ R3-X Rgr-COOM wherein R3 is ahydrocarbon radical, either aliphatic containing 6-18 carbon atoms, oraliphatic-aromatic consisting of a benzene ring or a naphthalene ringhaving an aliphatic radical of at least 6 carbon atoms attached thereto;X is 0303 or S03; and R, Y, Y1, R2 and M have been heretofore defined inFormula I.

According to this invention, I react a compound of Formula I with acompound of Formula II to provide the novel and highly useful compoundsof Formula III. In general this reaction is carried out in a solutioncontaining compounds I and II and to which a quantity of an acidic agentsuch as a strong mineral acid, as for example hydrochloric, sulphuric orits equivalent, has been added to lower the pH of the solution to avalue of approximately 7 to approximately 9 and while maintaining themass at a temperature between approximately -200 F. In this reactionunder the aforesaid conditions, the compounds of Formula III areproduced, said compounds having high water solubility in spite of thefact that the number of carbon atoms in R3 is 6 or more.

Such compounds of Formula III have an unexpected extremely highwater-solubility, while the corresponding.

salts of cationic compounds are water-insoluble, The resultant aqueoussolutioncan be used directly as asurface active agent, wetting agent ordetergent for the purposes indicated for the amino acid metal salts.While the quantities of the compound of Formula. I and compound ofFormula II may be equimolecular for good yield of compounds of FormulaIII, I may employ an excess of either, and in general the mole ratio ofa compound of Formula I to compound of Formula II may be 2 moles of theformer to 1-3 moles of thelat-ter.

One of the specific methods which I prefer to employ is carrying out anaspect of this invention is to first dissolve a compound of Formula I inwater and then the pH thereof is adjusted to approximately 1213(measured electrically) by the addition of aqueous caustic soda ifrequired so that when a compound of Formula II is added thereto, the pHof the solution of I and II will be at least and generally 105-11. Thetemperature of said solution is raised to 100200 F. and preferably infactory practice to approximately 140 F. Then a quantity of a compoundof Formula II is dissolved in water in a separate container and thissolution is added to said first solution and the mass is maintained insaid temperature range while being constantly stirred, and an acidicagent is added thereto to reduce the pH thereof to a value below 10 andin the range of approximately 7 to 9, and preferably of approximately8.2 to approximately 8.7. At the end of the acidic agent addition, thestirring is continued and the temperature of the mass maintained forabout 10-20 minutes after which the solution is allowed to cool and is afinished product.

The following are specific examples merely given by way of illustratingthe invention and are not to be taken by way of limitation, all partsbeing given by weight unless otherwise specified.

EXAMPLE 1 An aqueous solution of 330 parts of product A in 570 parts ofwateris heated to approximately 140" F. and its pH (measuredelectrically) is adjusted by the addition of aqueous caustic soda to12-13. While being constantly stirred and maintained at thattemperature, there is added a solution of 290 parts of sodium salt oflauryl sulfate:

in 450 parts of water. Then while stirring and the temperature ismaintained there is added thereto between about 30-40 parts ofhydrochloric acid solution (32%) whereby the pH of the mass is loweredto a value in the range of 8.2 to 8.7. Stirring is continued and thetemperature maintained for about 10 minutes more. The resultant productis a solution of the novel reaction product having the followingformula:

Employ the same procedure and components as set forth in Example 1,except that only about 150 parts of the sodium salt of lauryl sulfateare used. In this instance, t-he resultant product is a solution of thenovel reaction product whose structural formula is shown in Example 1together with unreacted product A used, in the approximate proportion oftwo parts of the former to one of the latter.

Employ the same procedure as that set forth in Example 1, but; employthe components indicated in the following Examples 3-36; the quantity ofhydrochloric acid solution (32%) is variable to lower the pH to valuesindicated in Example 1 to obtain the novel reaction products of saidExamples 3-36.

8 EXAMPLE: 3

409 parts of product B in 615 parts of water.

parts of stearyl sulfonate sodium salt:

CraHsw-SOs-Na in 700 parts of water.

FORMULA OF NOVEL REACTION PRODUCT C rsHsr-S Os EXAMP 410 parts ofproduct C in 615 parts of water. parts of dodecyl benzene sulfonatesodium salt:

in 500 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CIHAO CHr-C O ONB EXAMPLE 5 384 partsof product D in 576 parts of water. parts of hexylnaphthene sulfonatesodium salt:

S O r-Na OaHrs in 450 parts of water FORMULA OF NOVEL REACTION PRODUCTEXAMPLE 6 470 parts of product E in 705 parts of water.

parts of hexyl sulfate sodium salt:

CsHis-OS in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT EXAMPLE 7 in 600 parts of water.

FORMULA on NOVEL REACTION rnopuc'r oflukoo O Na OK -e ONa cunt-c 00mEXAMPLE 8 I 544 parts of product G in 816 parts of water. parts of octylbenzene sulfonate potassium salt:

CaH17--C6H4-SOa-K in 500 parts of water.

FORBIULA OF NOVEL REACTION PRODUCT CzHr-COONB.

OrzH2s-NCH2-C O ONa GHQCQHi-C o ONa CsH17-CaH4SOa EXAMPLE 9 230 parts ofProduct H in 345 parts of water. parts of decyl sulfonate sodium salt:

C10H21-SOa--Na in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT OHzCHOHCHzOH C9HmN-CH:COON3 CHu-OOONaCHEM-S03 EXAMPLE 10 602 parts of product I in 903 parts of water. partsof heptyl benzene sulfonate sodium salt:

C'1H15-CsH4SOsNa in 450 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CHz-COOK O9HiaCuH4-NCH2C OK CzHr-COOKC 7H1 CuH4S Os EXAMPLES 11-18 1 mole parts of products B to Irespectively in water measuring one and one half times the weights ofsaid products B to I respectively employed. 1 mole parts (290 parts) ofsodium salt of lauryl sulfate in 450 parts of water.

The resulting novel reaction products consist respectively of saidproducts B to I, but with the halogen atoms thereof replaced by theradical C12H25OSO3 in the same manner as shown in the structural formulaof the novel reaction product of Example 1, wherein the halogen atom ofproduct A is replaced by C12H2s-O-SO3.

EXAMPLES 19-29 Employing 270 parts of lauryl sulfonate in place of thelauryl sulfate of Examples 1 and 11-18 there are produced novel reactionproducts the same as those examples except that C12H25SO3 is substitutedfor the C12H25OSO3 therein.

EXAMPLES 30-40 Employing 330 parts of dodecyl benzene sulfonate sodiumsalt in 500 parts of water. 1 mole parts of products A, B, and C-I thereare produced reaction products in which C12H25--C6H4-SO3 replace thehalogen of said products.

It is to be understood that any of the products A-I, which are shownherein merely as illustrative examples of the starting materials ofFormula I may be reacted with any of the specific sulfate or sulfonatesalts which are shown herein merely as illustrative examples ofreactants of Formula II to produce novel compounds of Formula III. I

It is also to be understood that when either $03 or 0503 is used in thespecification or claims, it is meant to indicate either one or the otherbecause of their obvious equivalency; it is also to be understood thatthe use of Na in the specification and claims is meant to indicate anyof the other alkali metals because of their obvious equivalency, and itis also to be understood that aliphatic as employed in the specificationand claims in definition of R is meant to include straight and alsobranch chain aliphatic and cycloaliphatic. 7

It is also to be understood that instead of first adjusting the pH ofthe compound of Formula I to 12-13 before the addition of the compoundof Formula II, any other method may be employed to obtain the conditionwhereby the pH of the solution of I and II is at least 10 and preferably10.5-11 before the addition of the acidic agent to lower the pH of themass to approximately 7 to approximately 9. For example, I and II may bedissolved together and this solution may by the addition of caustic sodawhen required have its pH adjusted. to at least 10, and then at -200 F.is ready for the addition of the acidic agent to lower its pH toapproximately 7 to approximately 9. If desired, the required amount ofacidic agent may be added either before or after the solution at pH ofat least 10 is brought to a temperature in the range of 100-200 F.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions which embody the invention maybe made without departing from its scope, it is intended that all mattercontained in the description shall be interpreted as illustrative andnot in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which as amatter of language in which R is a hydrocarbon radical selected from thegroup consisting of aliphatic hydrocarbon radicals of 6-18 carbon atoms,aliphatic-aromatic hydrocarbon radicals of 6-18 carbon atoms, with thealiphatic portion thereof having at least 3 carbon atoms; Y and Y1 areeach selected from the class consisting of Re and Rz-COOM; R2 isselected from the class consisting of (a) hydroxy substituted aliphatichydrocarbon groups of 1-12 carbon atoms, (b) aliphatic ether groups,each of said groups containing at least one ether linkager therein andotherwise being hydrocarbons of 2-12 carbon atoms, (c) aliphatic ethergroups, each of said groups containing at least one ether linkagertherein and otherwise being hydroxy substituted hydrocarbons of 2-12carbon atoms, (d) aliphatic, aromatic and aromatic-aliphatic groups of1-12 carbon atoms; Rs se lected from the class consisting of monovalentradicals otherwise defined in (a)-( d); R3 is selected from the classconsisting of aliphatic hydrocarbon radicals of 6-18 carbon atoms, andaliphatic-aromatic hydrocarbon radicals or" 6-18 carbon atoms consistingof benzene and naphthalene groups, each having an aliphatic hydrocarbonradical of at least 6 carbon atoms attached thereto; X is selected fromthe class consisting of S03 and 0303; and M is an alkali metal.

2. A compound of the following formula:

3. A compound of the following formula:

' onl -V0001:

O0Hm-CsH4-N-GH2G O O K O 1H15C (Hg-S Os 4. A compound of the following Iformula:

0 H3 C12 2aNC Ha GHaC O O Na nHzr-CeHa-S O 3 5 A compound of thefollowing formula:

CH2C O O Na C lzHgr-N-CeHb {311E140 CHr-O O ONa G1z Co u-SO2 12 6. Acompound of the following formula:

CH2C O ONa QHW OBI A N CHQ C O O Na 6 C2HlOH CGHXJ References Cited inthe file of this patent UNITED STATES PATENTS 15 2,097,640 Piggott Nov.2, 1937 FOREIGN PATENTS 208,288 Switzerland Apr. 16, 1940

1. A COMPOUND OF THE FOLLOWING FORMULA: